Hydrophobically modified polyamine scale inhibitors

ABSTRACT

Hydrophobically modified Si-containing polyamines are useful for treating scale in industrial process streams. Preferred hydrophobically modified Si-containing polyamines are particularly useful for treating aluminosilicate scale in difficult-to-treat industrial process streams, such as in the Bayer alumina process streams, nuclear waste streams and kraft paper mill effluent streams.

RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 13/786,871, filed Mar. 6, 2013, which is acontinuation application of U.S. patent application Ser. No. 13/109,643,filed on May 17, 2011, now issued as U.S. Pat. No. 8,450,452, which is adivisional application of U.S. patent application Ser. No. 11/870,925,filed on Oct. 11, 2007, now issued as U.S. Pat. No. 7,999,065, whichclaims priority to U.S. Provisional Patent Application No. 60/829,411,filed on Oct. 13, 2006. The aforementioned applications are incorporatedby reference herein in their entirety.

FIELD

This invention relates to polyamines and methods of using them fortreating scale in various industrial process streams. Preferredembodiments relate to hydrophobically modified Si-containing polyaminesthat have been found to be particularly useful for treatingaluminosilicate scale in difficult-to-treat industrial process streams,such as in the Bayer alumina process, nuclear waste streams and kraftpaper mill effluent streams.

DESCRIPTION OF THE RELATED ART

The formation of scale is a problem in a number of industrial processstreams. Scale is a solid material that generally forms on the surfacesof equipment that are exposed to aqueous process streams. Scaletypically contains inorganic materials having relatively low aqueoussolubility, including for example various hydrated sodiumaluminosilicate materials such as amorphous aluminosilicates (e.g.,aluminosilicate hydrogel), zeolites, sodalites and canerinites. Theremoval of scale by mechanical methods, e.g., by scraping, is oftenundesirable because such procedures may involve considerable expense interms of process downtime, and may be impractical where the scale formson surfaces of the process equipment that are difficult to access.

A number of chemical treatments have been developed to remove scaleand/or inhibit the formation of scale in various industrial processstreams. Such chemical treatments are generally applied by intermixingthe treatment chemical with the process stream, thus allowing treatmentof surfaces that are difficult to access and reducing or eliminatingdowntime. A number of Si-containing polymers have been developed inrecent years and applied to the treatment of scale. See, e.g., U.S. Pat.No. 6,814,873; U.S. Patent Publication Nos. 2005/0010008, 2004/0162406,2006/0124553, 2004/0162406, 2004/0011744, and 2005/0274926; and WO 2004009606. The foregoing patent publications are hereby incorporated byreference in their entireties, and particularly for the purpose ofdescribing various types of scale, as well as particular Si-containingpolymers and their use as anti-scalants in certain industrial processstreams:

The Si-containing polymers and methods of using them described aboverepresent a significant advance in the art, but have not completelysolved the problem of scale formation in industrial process streams.Difficult-to-treat industrial process streams are particularly vexing.For example, there is a long-felt need for chemical treatments andmethods of reducing and/or inhibiting scale in process streams thatcontain a relatively high level of sulfate, finely dispersed iron oxide(e.g., “red mud”), finely dispersed sodalite, and/or combinednitrate/nitrite.

A variety of Si-containing polymers have been developed for otherpurposes, but without any particular motivation to apply suchnon-analogous art to the treatment of scale. See, e.g., U.S. Pat. Nos.3,560,543; 5,354,829; 6,262,216; 6,410,675; 6,429,275; 6,486,287; and6,743,882; U.S. Patent Publication No. 2006/0159975; Canadian CA2,193,155; Yang et al, Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004,49(2), 599-600; and Macromol. Symp. 2004, 210, 329.

SUMMARY

Novel Si-containing polymers and methods have now been developed for thetreatment of scale in industrial process streams. Surprisingly, it hasbeen found that relatively hydrophobic Si-containing polymers mayprovide substantially higher performance than otherwise comparablepolymers of lesser hydrophobicity.

An embodiment provides polymer comprising a recurring unit of theformula (I) and a recurring unit of the formula (II):

wherein:

T and E are each independently a first optionally substitutedhydrocarbyl radical comprising from about 2 to about 40 carbons;

Q is H or a second optionally substituted hydrocarbyl radical comprisingfrom about 1 to about 20 carbons;

A¹ and A² are each independently a direct bond or an organic connectinggroup comprising from about 1 to about 20 carbons;

R″═H, optionally substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂aryl, optionally substituted C₇-C₂₀ aralkyl, optionally substitutedC₂-C₂₀ alkenyl, Group I metal ion, Group II metal ion, or NR¹ ₄, whereeach R¹ is independently selected from H, optionally substituted C₁-C₂₀alkyl, optionally substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀aralkyl, and optionally substituted C₂-C₂₀ alkenyl; and

the polymer has a weight average molecular weight of at least about 500;

-   -   with a first proviso that when A²-Q is H, at least one of T and        E comprises 4 or more carbon atoms;    -   with a second proviso that when A²-Q is not H, at least one of T        and E comprises 2 or more carbon atoms;    -   with a third proviso that Q does not contain a Si(OR″)₃ group;    -   with a fourth proviso that A² is not unsubstituted —C(═O)-alkyl;        and    -   with a fifth proviso that when Q is OH or NH₂, A¹ and A² are not        both alkylene.

Another embodiment provides a composition comprising a polymericreaction product of at least a polyamine, a first nitrogen-reactivecompound, and a second nitrogen-reactive compound, the polymericreaction product having a weight average molecular weight of at leastabout 500, wherein:

-   -   the first nitrogen-reactive compound comprises a —Si(OR″)₃ group        and a nitrogen-reactive group, where R″═H, optionally        substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,        optionally substituted C₇-C₂₀ aralkyl, optionally substituted        C₂-C₂₀ alkenyl, Group I metal ion, Group II metal ion, or NR¹ ₄,        each R¹ being independently selected from H, optionally        substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,        optionally substituted C₇-C₂₀ aralkyl, and optionally        substituted C₂-C₂₀ alkenyl;    -   the second nitrogen-reactive compound comprises a        nitrogen-reactive group and does not contain a Si(OR″)₃ group;        and    -   at least one of the polyamine and the second nitrogen-reactive        compound comprises an optionally substituted hydrocarbyl radical        comprising from about 2 to about 40 carbons.

Another embodiment provides a method for reducing or eliminating scalein an industrial process, comprising adding a polymer or composition asdescribed herein to the process.

Another embodiment provides a method for treating scale in adifficult-to-treat process stream, comprising intermixing a polymer witha process stream in an amount effective to reduce or eliminatealuminosilicate scale in the process stream,

-   -   wherein the process stream comprises at least one selected from        a sulfate level of at least about 1 g/L, a finely dispersed iron        oxide level of at least about 20 mg/L, a finely dispersed        sodalite level of at least about 20 mg/L, and a combined        nitrate/nitrite concentration of at least about 0.5 molar; and    -   wherein the polymer comprises a recurring unit of the        formula (I) and a recurring unit of the formula (II):

-   -   wherein:    -   T and E are each independently a first optionally substituted        hydrocarbyl radical comprising from about 2 to about 40 carbons;    -   Q is H or a second optionally substituted hydrocarbyl radical        comprising from about 1 to about 20 carbons;    -   A¹ and A² are each independently a direct bond or an organic        connecting group comprising from about 1 to about 20 carbons;        and    -   R″═H, optionally substituted C₁-C₂₀ alkyl, optionally        substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀ aralkyl,        optionally substituted C₂-C₂₀ alkenyl, Group I metal ion, Group        II metal ion, or NR¹ ₄, where each R¹ is independently selected        from H, optionally substituted C₁-C₂₀ alkyl, optionally        substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀ aralkyl,        and optionally substituted C₂-C₂₀ alkenyl.        -   These and other embodiments are described in greater detail            below.

DETAILED DESCRIPTION

Terms such as “treatment” and “treating”, in the context of describingmethods for the treatment of scale, are broad terms that are used hereinin their ordinary sense as understood by those skilled in the art, andthus include methods that result in the inhibition and/or prevention ofscale formation, as well as reduction, removal and/or elimination ofexisting scale.

The term “scale” is a broad term that is used herein in its ordinarysense as understood by those skilled in the art, and thus includesvarious primarily or completely inorganic deposits formed on thesurfaces of equipment exposed to industrial process streams. Examples ofscale include hydrated sodium aluminosilicate materials such asamorphous aluminosilicates (e.g., aluminosilicate hydrogel), zeolites,sodalites and canerinites.

Terms used herein to describe chemical materials, such as“anti-scalant”, “scale inhibitor”, “scale reducing additive”, etc., arebroad terms that are used herein in their ordinary sense as understoodby those skilled in the art and thus include chemical materials (such aspolymers) that are useful for treating scale.

The term “polymer” is a broad term that is used herein in its ordinarysense as understood by those skilled in the art, and thus includescopolymers. Reference herein to the molecular weight of a polymer isunderstood to be a reference to weight average molecular weight asmeasured by size exclusion chromatography (light scattering detection).In various embodiments, Si-containing polymers (including, for example,the polymer P1 described herein) can have a molecular weight of at leastabout 500, at least about 1,000, at least about 2,000, or at least about5,000. In some embodiments, higher or lower molecular weights arepreferred. Although some polymers may be referred to herein as being“hydrophobically modified”, it will be understood that this term is usedfor the sake of convenience, and that such polymers are not limited tothose produced by hydrophobic modification of a pre-existing polymer.

The terms “hydrocarbon” and “hydrocarbyl” are broad terms that are usedherein in their ordinary sense as understood by those skilled in theart, and thus include organic compounds or radicals consistingexclusively of the elements carbon and hydrogen. These moieties includealkyl, alkylene, alkenyl, alkynyl, and aryl moieties. These moietiesalso include alkyl, alkenyl, alkynyl, and aryl moieties substituted withother aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryland alkynaryl. Unless otherwise indicated, these moieties preferablycomprise 1 to 40 carbon atoms. Hydrocarbyl radicals may be substitutedwith various groups that do not consist exclusively of the elementscarbon and hydrogen, and thus a substituted hydrocarbyl radical maycontain one or more heteroatoms such as oxygen and/or nitrogen.

The term “substituted”, whether preceded by the term “optionally” ornot, is a broad term that is used herein in its ordinary sense asunderstood by those skilled in the art. “Substituted” thus includesreplacement of one or more hydrogen radicals in a given structure withone or more substituent groups, which may be any permissible organicsubstituents of the given structure. Examples of substituents that maybe permissible for a given structure include hydroxy; C₁₋₁₀ alkyl; C₁₋₁₀alkenyl; allyl; halogen; C₁₋₁₀ haloalkyl; C₁₋₁₀ alkoxy; hydroxy C₁₋₁₀alkyl; carboxy; C₁₋₁₀ carboalkoxy (also referred to as alkoxycarbonyl);C₁₋₁₀ carboxyalkoxy; C₁₋₁₀ carboxamido (also referred to asalkylaminocarbonyl); cyano; formyl; C₁₋₁₀ acyl; nitro; amino; C₁₋₁₀alkylamino; C₁₋₁₀ dialkylamino; anilino; mercapto; C₁₋₁₀ alkylthio;sulfoxide; sulfone; C₁₋₁₀ acylamino; amidino; phenyl; benzyl;heteroaryl; heterocycle; phenoxy; benzoyl; benzoyl substituted withamino, hydroxy, methoxy, methyl or halo; benzyloxy and heteroaryloxy.When the group that is substituted contains an alkyl segment, twohydrogen atoms on the same carbon atom may be replaced by a singlesubstituent double bonded to the carbon atom, e.g, oxo (═O).

Various compositions are described herein, including polymers andpolymeric reaction products, along with various methods for using suchcompositions. It will be understood by those skilled in the art that thevarious compositions described herein may be used in any of thedescribed methods, and that the described methods may employ any of thedescribed compositions. Thus, it will be understood that the inventionsdescribed herein are not limited to the descriptions of the particularembodiments.

Compositions and Methods of Making them

An embodiment provides a polymer comprising a recurring unit of theformula (I) and a recurring unit of the formula (II):

-   -   wherein:    -   T and E are each independently a first optionally substituted        hydrocarbyl radical comprising from about 2 to about 40 carbons;    -   Q is H or a second optionally substituted hydrocarbyl radical        comprising from about 1 to about 20 carbons;    -   A¹ and A² are each independently a direct bond or an organic        connecting group comprising from about 1 to about 20 carbons;        and    -   R″═H, optionally substituted C₁-C₂₀ alkyl, optionally        substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀ aralkyl,        optionally substituted C₂-C₂₀ alkenyl, Group I metal ion, Group        II metal ion, or NR¹ ₄, where each R¹ is independently selected        from H, optionally substituted C₁-C₂₀ alkyl, optionally        substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀ aralkyl,        and optionally substituted C₂-C₂₀ alkenyl.

The term “polymer P1” may be used herein to refer to polymers comprisinga recurring unit of the formula (I) and a recurring unit of the formula(II). In an embodiment, the polymer P1 comprises recurring units of theformula (I) in which R″ is a Group I metal ion (e.g., Na), a Group (II)metal ion (e.g., K) and/or NR¹ ₄ (e.g., ammonium). In variousembodiments, the polymer P1 may be further described as being subject toone or more of the following provisos: a first proviso that when A²-Q isH, at least one of T and E comprises 4 or more carbon atoms; a secondproviso that when A²-Q is not H, at least one of T and E comprises 2 ormore carbon atom; a third proviso that Q does not contain a Si(OR″)₃group; a fourth proviso that A² is not unsubstituted —C(═O)-alkyl;and/or a fifth proviso that when Q is OH or NH₂, A¹ and A² are not bothalkylene. It will be understood that the polymer P1 may comprise otherrecurring units as well. For example, in an embodiment, a polymercomprising a recurring unit of the formula (I) and a recurring unit ofthe formula (II) further comprises a recurring unit of the formula—((CH₂)_(n)—NH)—, wherein n is an integer in the range of about 2 toabout 10. The amounts of recurring unit in the polymer P1 may vary overa broad range. For example, in an embodiment, the polymer P1 comprisesat least about 0.1 mole percent, preferably at least about 1 molepercent of recurring units of the formula (I) and at least about 0.1mole percent, preferably at least about 1 mole percent of recurringunits of the formula (II), based on total moles of recurring units inthe polymer P1.

As indicated above, the recurring units of the formulae (I) and (II) inthe polymer P1 include A¹ and A², which are each independently a directbond or an organic connecting group comprising from about 1 to about 20carbons. Examples of suitable organic connecting groups include those inwhich A¹ and A² are each independently represented by -A³-A⁴-A⁵-A⁶-,where:

-   -   A³=a direct bond, NR′ or O, where R′ is H or C₁₋₃ alkyl;    -   A⁴=a direct bond, C═O, optionally substituted C₁-C₁₀ alkylene,        or optionally substituted C₆-C₁₂ aryl;    -   A⁵=a direct bond, O, NR′″, amide, urethane or urea, where R′″ is        H or C₁₋₃ alkyl; and    -   A⁶=a direct bond, O, optionally substituted C₁-C₂₀ alkyl,        optionally substituted C₂-C₂₀ alkenyl or optionally substituted        C₇-C₂₀ aralkyl.

Examples of organic connecting groups A¹ and A² include —CH(OH)—CH₂—,—CH₂—CH(OH)—, —CH(OH)—CH₂—O—, —CH₂—CH(OH)—O—, —CH₂—CH(OH)—CH₂—O—,—C(═O)—CH(CO₂M)-, —C(═O)—CH(CH₂CO₂M)- and —C(═O)—CH₂—CH(CO₂M)-, where Mis H, a metal cation such as Na, an ammonium cation such astetraalkylammonium or NH₄, or an organic group such as optionallysubstituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl, optionallysubstituted C₇-C₂₀ aralkyl, or optionally substituted C₂-C₂₀ alkenyl. Ina preferred embodiment, at least one of the organic connecting groups A¹and A² is —CH₂—CH(OH)—CH₂—O—.

Those skilled in the art will appreciate that hydrophobicity may beincorporated in various ways into the polymer P1. In an embodiment, atleast one of the first and second hydrocarbyl radicals T, E and Q isoptionally substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,optionally substituted C₇-C₂₀ aralkyl, or optionally substituted C₂-C₂₀alkenyl. For example, in some embodiments, at least one of the firsthydrocarbyl radicals T and E is selected from —(CH₂)₂— and ahydroxypropylene, e.g., —CH₂—CH(OH)—CH₂—. Q is preferably selected frompropyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, C₇-C₂₀alkylphenyl (e.g., cresyl, nonylphenyl), cetyl, octenyl, and octadecyl.In some embodiments, Q is selected from butyl, 2-ethylhexyl, phenyl,cresyl, nonylphenyl, cetyl, octenyl, and octadecyl. When A²-Q is H, Tand E are preferably each independently selected from optionallysubstituted C₂-C₈ alkylene, isophorone and hydroxypropylene.

Another embodiment provides a composition comprising a polymericreaction product of at least a polyamine, a first nitrogen-reactivecompound, and a second nitrogen-reactive compound, the polymericreaction product having a weight average molecular weight of at leastabout 500, wherein:

-   -   the first nitrogen-reactive compound comprises a —Si(OR″)₃ group        and a nitrogen-reactive group, where R″═H, optionally        substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,        optionally substituted C₇-C₂₀ aralkyl, optionally substituted        C₂-C₂₀ alkenyl, Group I metal ion, Group II metal ion, or NR¹ ₄,        each R¹ being independently selected from H, optionally        substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,        optionally substituted C₇-C₂₀ aralkyl, and optionally        substituted C₂-C₂₀ alkenyl;    -   the second nitrogen-reactive compound comprises a        nitrogen-reactive group and does not contain a Si(OR″)₃ group;        and    -   at least one of the polyamine and the second nitrogen-reactive        compound comprises an optionally substituted hydrocarbyl radical        comprising from about 2 to about 40 carbons.

The term “PRP1” may be used herein to refer to such a polymeric reactionproduct. Various polyamines may be used to make PRP1. For example, in anembodiment, the polyamine comprises a recurring unit of the formula—(CH₂)_(r)—NR″″)—, where r is an integer in the range of 1 to about 20and R″″ is H, optionally substituted C₁-C₂₀ alkyl, optionallysubstituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀ aralkyl, oroptionally substituted C₂-C₂₀ alkenyl. In another embodiment, thepolyamine comprises a (NR⁴ ₂)-J-(NR⁴ ₂) moiety, wherein J is anoptionally substituted hydrocarbyl fragment comprising from about 2 toabout 40 carbons; and each R⁴ is independently H, optionally substitutedC₁₋₈ alkyl, or optionally substituted C₆₋₁₀ aryl. Preferably, thehydrocarbyl fragment J is optionally substituted C₃-C₂₀ alkyl,optionally substituted C₃-C₂₀ alkenyl group or optionally substitutedC₃-C₂₀ aryl. Preferably, the polyamine is a C₆-C₂₀ aliphatic diamine.Examples of suitable polyamines include polyethyleneimine,triethylenetetramine, 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,5-diaminopentane, 1,5-diaminohexane,1,8-diaminooctane, diaminoisophorone, aminoaniline, andaminomethylbenzylamine.

Various Si-containing nitrogen-reactive compounds may be used to makePRP1. Suitable Si-containing nitrogen-reactive compounds comprise anitrogen-reactive group, e.g., containing suitably configured halide,sulfate, epoxide, isocyanates, anhydride, carboxylic acid, and/or acidchloride functionalities. Examples of suitable nitrogen-reactive groupsinclude alkyl halide (e.g., chloropropyl, bromoethyl, chloromethyl, andbromoundecyl) epoxy (e.g., glycidoxypropyl, 1,2-epoxyamyl,1,2-epoxydecyl or 3,4-epoxycyclohexylethyl), isocyanate (e.g.,isocyanatopropyl or isocyanatomethyl that react to form a urea linkage),anhydride (e.g., malonic anhydride, succinic anhydride) and combinationsof such groups, e.g., a combination of a hydroxyl group and a halide,such as 3-chloro-2-hydroxypropyl. Triethoxysilylpropylsuccinicanhydride, glycidoxypropyl trimethoxysilane and chloropropyltrimethoxysilane are examples a nitrogen-reactive compounds thatcomprise a —Si(OR″)₃ group and a nitrogen-reactive group. A variety ofsuch compounds are known to those skilled in the art, see, e.g., U.S.Pat. No. 6,814,873, which is hereby incorporated by reference andparticularly for the purpose of describing such compounds and methods ofincorporating them into polymers.

Various nitrogen-reactive compounds that comprise a nitrogen-reactivegroup and that do not contain a Si(OR″)₃ group may be used to make PRP1.Suitable nitrogen-reactive compounds include those containing one ormore of the nitrogen-reactive groups mentioned above. Non-limitingexamples of nitrogen-reactive compounds that comprise anitrogen-reactive group and that do not contain a Si(OR″)₃ group includeC₁-C₂₀ alkyl halides (e.g., chlorides, bromides, and iodides of alkylssuch as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl), alkenylhalides such as allyl chloride, aralkyl halides such as benzyl chloride,alkyl sulfates such as dimethyl sulfate, compounds containing at leastone epoxide group (e.g., glycidyl alcohols, phenols, and amines), andcompounds containing an anhydride group e.g., alkenyl malonic anydridesand/or alkenyl succinic anhydrides. Examples of preferred secondnitrogen-reactive compounds include dimethylsulfate, chlorooctane,chlorohexane, benzyl chloride, epichlorohydrin, glycidyl4-nonylphenylether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,phenyl glycidyl ether, C₁₂-C₁₄ alkyl glycidyl ether, cresyl glycidylether, octenylsuccinic anhydride and octadecenylsuccinic anhydride. Insome embodiments, the second nitrogen-reactive compound (comprising anitrogen-reactive group and not containing a Si(OR″)₃ group) comprisesat least two nitrogen-reactive functionalities, which may be the same ordifferent from one another.

A composition that comprises PRP1 may comprise the polymer P1. Forexample, in an embodiment, PRP1 comprises a recurring unit of theformula (I) and a recurring unit of the formula (II), wherein T, E, Q,A¹, A² and R″ have the same meanings as set forth above. It will beunderstood that the first, second, third, fourth and fifth provisosdescribed above with respect to the polymer P1, each alone or togetherin any combination, may apply in the context of a PRP1 that comprisesthe polymer P1.

The polymers and compositions described herein can be made in variousways. For example, PRP1 and the polymer P1 may be prepared by reactingtogether under suitable conditions, in any order, a polyamine, a firstnitrogen-reactive compound, and a second nitrogen-reactive compound, asthose materials are described above. It will be understood that each ofthe polyamine, the first nitrogen-reactive compound, and the secondnitrogen-reactive compound may comprise a mixture of particularcompounds. Those skilled in the art can identify suitable reactionconditions and prepare a wide variety of polymers and compositions(e.g., PRP1 and the polymer P1), using routine experimentation informedby the guidance provided herein.

In a first embodiment of a method of making PRP1 and the polymer P1, abackbone polyamine (e.g., polyethyleneimine), typically having arelatively higher molecular weight (as compared to the polyfunctionalamine monomer described below), is functionalized by reacting with thefirst nitrogen-reactive compound (to thereby incorporate —Si(OR″)₃groups), and the second nitrogen-reactive compound (to therebyincorporate or increase hydrophobicity). In many cases, the overalllength of the backbone polyamine is not increased, although themolecular weight of the polyamine is increased by the attachment of theSi-containing group and the non-Si-containing hydrophobic group.Molecular weight may also be increased by crosslinking. In many casesthe reaction is not a polymerization per se, but is instead a polymerfunctionalization (with possible crosslinking). The product of such areaction (which may be PRP1 or P1) may be referred to herein as asilanized hydrophobically modified polyamine. Examples 1-6 belowillustrate methods for making polymers in accordance with this firstembodiment.

In a second embodiment of a method of making PRP1 and the polymer P1, arelatively low molecular weight polyamine monomer or oligomer (e.g., apolyfunctional amine monomer such a triethylenetetramine) is reactedwith the first nitrogen-reactive compound and the secondnitrogen-reactive compound. In this second embodiment, at least one ofthe first nitrogen-reactive compound and the second nitrogen-reactivecompound comprises at least two nitrogen-reactive functionalities, andthe overall formation of the resulting polymer may be considered toinvolve a condensation polymerization between the polyamine and thefirst/and or second nitrogen-reactive compound(s), along with possiblecrosslinking. Examples 7-15 below illustrate methods for making polymersin accordance with this second embodiment.

Methods of Treating Scale

The polymers and compositions described herein (e.g., PRP1 and thepolymer P1, including all of the embodiments described herein) areuseful for treating scale (e.g., aluminosilicate scale) in variousindustrial process streams, e.g., Bayer process streams, boiler water,nuclear waste process streams, a papermaking process streams. Methodsfor treating scale may be carried out by intermixing the polymer withthe process stream in an amount effective to reduce or eliminate scale.In preferred embodiments, such methods unexpectedly provide significantimprovements in scale reduction. An embodiment provides a method forreducing or eliminating scale in an industrial process, comprisingadding a polymer and/or composition as described herein to the process,preferably in an amount effective to reduce or eliminate scale.Typically the amount of polymer and/or composition that is effective toreduce or eliminate scale (e.g., aluminosilicate scale) in the processstream is in the range of about 1 ppm to about 500 ppm, by weight basedon the process stream, although in some cases smaller or larger amountsmay be effective. Those skilled in the art can identify effectiveamounts of polymer and/or composition for a particular process steam,using routine experimentation informed by the guidance provided herein.

In preferred embodiments, the polymers and/or compositions areparticularly useful for treating aluminosilicate scale indifficult-to-treat industrial process streams, such as in the Bayeralumina process, nuclear waste streams and kraft paper mill effluentstreams. An embodiment provides a method for treating scale in adifficult-to-treat process stream, comprising intermixing a polymer witha process stream in an amount effective to reduce or eliminatealuminosilicate scale in the process stream. Those skilled in the artare familiar with difficult-to-treat process streams, which may have anyor more, in any combination, of the following characteristics: a sulfatelevel of at least about 1 g/L, a finely dispersed iron oxide level of atleast about 20 mg/L, a finely dispersed sodalite level of at least about20 mg/L, and/or a combined nitrate/nitrite concentration of at leastabout 0.5 molar.

EXAMPLES

Test Procedure A: A difficult-to-treat liquor is prepared and used totest the polymers described in the Examples below. Thedifficult-to-treat liquor is made by adding 12 ml of a sodium silicatesolution (27.7 g/L of a sodium silicate solution which is 28.9% SiO₂) to108 ml of a sodium aluminate solution that contains sodium aluminate,excess sodium hydroxide, sodium carbonate, and sodium sulfate. Aftermixing, the solution contains 0.8 g/L SiO₂, 45 g/L Al₂O₃, 150 g/L NaOH,60 g/L Na₂CO₃, and 20 g/L Na₂SO₄. Aliquots of this solution are placedinto 125 ml polyethylene bottles. A polymer described in the Examplesbelow is also added to the bottle (generally the polymer is added in theform of a solution containing 0.1-10% of active reagent); blank(control) samples are also prepared without the polymer. The sealedbottles are heated with agitation at 100° C. for 18±2 hours. At the endof the 18 hours, the bottles are opened and the solution is filtered.With no polymer additive to the system (blank tests), considerablealuminosilicate is formed and is recovered on the filter paper. Thetotal aluminosilicate precipitated in the blank tests is typically about200 mg. In the Examples below, the amount of aluminosilicateprecipitated is a measure of antiscalant activity and is expressed as apercentage of the aluminosilicate that formed in the corresponding blankexperiments that were part of the same set of tests. Results obtainedusing comparative polymers are indicated by a “*” in the Tables below.

This difficult-to-treat liquor contains relatively high levels ofsulfate and carbonate and is considered more difficult to treat than theliquor described in U.S. Pat. No. 6,814,873, and thus represents aparticularly difficult-to-treat Bayer liquor. Only about 150 mg ofprecipitate is formed in the blank tests with the liquor described inU.S. Pat. No. 6,814,873, whereas a larger amount (typically about 200mg) of precipitate forms in the blank tests with the difficult-to-treatliquor used to test the polymers described in the Examples below.

Test Procedure B: This procedure is conducted in the same manner as TestProcedure A except that 150 mg/L of “red mud” solids are added to thetest liquor. These red mud solids are obtaining by washing, drying andgrinding actual red mud waste obtained from a Bayer alumina plant.

Test Procedure C: This procedure is conducted in the same manner as TestProcedure A except that 50 mg/L of sodalite solids are added to the testliquor and the test is run for only four hours instead of 18. Thesodalite solids are made by reacting kaolin with sodium hydroxide.

Example 1

Product A (comparative) is made as follows: 10.00 g of polyethyleneimine(Lupasol WF from BASF) is mixed with about 2.19 g of glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight). Themixture is heated at 75° C. for 16 hours to give a polymeric reactionproduct. Aqueous NaOH solution (20 g/L) is then added to hydrolyze themethoxysilane groups to —Si—ONa groups to make a 10% solution of thesodium salt.

Product B1 (hydrophobically modified) is made in a similar fashion asfollows: 10.00 g of polyethyleneimine (Lupasol WF from BASF) is mixedwith 2.19 g glycidoxypropyltrimethoxysilane (4 mole % based on the PEIrecurring unit weight) and 0.71 g chlorooctane (2 mole % based on thePEI recurring unit weight). The mixture is heated at 75° C. for 16 hoursto give a polymeric reaction product. Aqueous NaOH solution (20 g/L) isthen added to make a 10% solution of the sodium salt.

Product B2 (hydrophobically modified) is made as follows: 8.66 g ofpolyethyleneimine (Lupasol WF from BASF) is mixed with 1.90 gglycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurringunit weight) and 1.34 benzyl chloride (5.26 mole % based on the PEIrecurring unit weight). The mixture is heated at 75° C. for 16 hours togive a polymeric reaction product. Aqueous NaOH solution (20 g/L) isthen added to make a 10% solution of the sodium salt.

Tests comparing Products A, B1 and B2 (Table 1) in accordance with TestProcedure A show that the relatively more hydrophobic Products B1 and B2give significantly better reduction in the amount of sodaliteprecipitated.

TABLE 1 % Sodalite Precipitated Dose No. Product 5 ppm 3 ppm 1A* A 19 351B B1 0.4 4.1 1C* A 12 1D B2 2.0

Example 2

Product C (hydrophobically modified) is made as follows: 10.00 g ofpolyethyleneimine (Lupasol WF made by BASF) is mixed with 2.19 gglycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurringunit weight) and 0.64 g glycidyl 4-nonylphenylether (1 mole % based onthe PEI recurring unit weight). The mixture is heated at 75° C. for 16hours to give a polymeric reaction product. Aqueous NaOH solution (20g/L) is then added to make a 10% solution of the sodium salt.

Tests comparing Products A and C (Table 2) in accordance with TestProcedure A show that the relatively more hydrophobic Product C givessignificantly better reduction in the amount of sodalite precipitated.

TABLE 2 % Sodalite Precipitated Dose No. Product 5 ppm 3 ppm 2A* A 12 322B C 0 4.9

Example 3

Product D (comparative) is made as follows: 5.00 g of polyethyleneimine(Lupasol PR 8515 from BASF) is mixed with about 1.1 g of glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight). Themixture is kept at room temperature for 16 hours, then heated at 75° C.for 4 hours to give a polymeric reaction product. Aqueous NaOH solution(20 g/L) is then added to hydrolyze the methoxysilane groups to —Si—ONagroups to make a 10% solution of the sodium salt.

Product E (hydrophobically modified) is made as follows: 5.00 g ofpolyethyleneimine (Lupasol PR 8515 from BASF) is mixed with 1.10 gglycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurringunit weight) and 0.64 g glycidyl 4-nonylphenylether (1 mole % based onthe PEI recurring unit weight). The mixture is kept at room temperaturefor 16 hours, then heated at 75° C. for 4 hours to give a polymericreaction product. Aqueous NaOH solution (20 g/L) is then added to make a10% solution of the sodium salt.

Products F and G are made in a similar fashion to Product E, except that1.61 g glycidyl 4-nonylphenylether (5 mole % based on the PEI recurringunit weight) is used to make Product F, and 3.21 g glycidyl4-nonylphenylether (10 mole % based on the PEI recurring unit weight) isused to make product G, instead of the amount of glycidyl4-nonylphenylether used to make Product E.

Tests comparing Products D, E, F and G (Table 3) in accordance with TestProcedure A show that the relatively more hydrophobic Products E, F andG give significantly better reduction in the amount of sodaliteprecipitated.

TABLE 3 % Sodalite Precipitated Dose No. Product 20 ppm 10 ppm 5 ppm 3ppm 3A* D 96 100 3B E 0.1 1.3 20 54 3C F 0 0.2 1.1 9.3 3D G 0 0 25 24

Example 4

Product H (comparative) is made as follows: 5.00 g of polyethyleneimine(Lupasol PR 8515 from BASF) is mixed with about 0.92 g of chloropropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight). Themixture is kept at room temperature for 16 hours, then heated at 75° C.for 4 hours to give a polymeric reaction product. Aqueous NaOH solution(20 g/L) is then added to hydrolyze the methoxysilane groups to —Si—ONagroups to make a 10% solution of the sodium salt.

Product I (hydrophobically modified) is made as follows: 5.00 g ofpolyethyleneimine (Lupasol PR 8515 from BASF) is mixed with 0.92 g ofchloropropyl trimethoxysilane (4 mole % based on the PEI recurring unitweight) and 1.46 g dimethylsulfate (10 mole % based on the PEI recurringunit weight). The mixture is kept at room temperature for 16 hours, thenheated at 75° C. for 4 hours to give a polymeric reaction product.Aqueous NaOH solution (20 g/L) is then added to make a 10% solution ofthe sodium salt.

Tests comparing Products H and I (Table 4) in accordance with TestProcedure A show that the relatively more hydrophobic Product I givessignificantly better reduction in the amount of sodalite precipitated.

TABLE 4 % Sodalite Precipitated Dose No. Product 100 ppm 300 ppm 4A* H80 7.9 4B I 4.3 0

Example 5

Product J (comparative) is made as follows: 5.00 g of polyethyleneimine(Lupasol PR 8515 from BASF) is mixed with about 1.65 g ofglycidoxypropyl trimethoxysilane (6 mole % based on the PEI recurringunit weight). The mixture is kept at room temperature for 16 hours, thenheated at 75° C. for 4 hours to give a polymeric reaction product.Aqueous NaOH solution (20 g/L) is then added to hydrolyze themethoxysilane groups to —Si—ONa groups to make a 10% solution of thesodium salt.

Products K-R (hydrophobically modified) are made as follows: 5.00 g ofpolyethyleneimine (Lupasol PR 8515 from BASF) is mixed with about 1.65 gof glycidoxypropyl trimethoxysilane (6 mole % based on the PEI recurringunit weight) and the amount of a second nitrogen-reactive compound (5mole % based on the PEI recurring unit weight) shown in Table 5. Themixtures are kept at room temperature for 16 hours, then heated at 75°C. for 4 hours to give polymeric reaction products. Aqueous NaOHsolution (20 g/L) is then added to hydrolyze the methoxysilane groups to—Si—ONa groups to make a 10% solution of the sodium salt.

Tests comparing Products J-R (Table 5) in accordance with Test ProcedureA show that the relatively more hydrophobic Products K-R givesignificantly better reduction in the amount of sodalite precipitated.

TABLE 5 % Sodalite Precipitated Dose No. Product SecondNitrogen-Reactive Compound (5 ppm) 5A* J None 100 5B K 4-nonylphenylglycidyl ether 0.5 5C L butyl glycidyl ether 83 5D M 2-ethylhexylglycidyl ether 1.1 5E N phenyl glycidyl ether 70 5F O C₁₂-C₁₄alkylglycidyl ether 8.4 5G P cresyl glycidyl ether 23 5H Qoctenylsuccinic anhydride 6.5 5I R octadecenylsuccinic anhydride 86

Example 6

Product S (comparative) is made as follows: 10.00 g of polyethyleneimine(Lupasol WF from BASF) is mixed with about 1.1 g of glycidoxypropyltrimethoxysilane (2 mole % based on the PEI recurring unit weight). Themixture is heated at 75° C. for 5 hours to give a polymeric reactionproduct. Aqueous NaOH solution (20 g/L) is then added to hydrolyze themethoxysilane groups to —Si—ONa groups to make a 10% solution of thesodium salt.

Product T (hydrophobically modified) is made as follows: 10.00 g ofpolyethyleneimine (Lupasol WF from BASF) is mixed with 1.10 gglycidoxypropyltrimethoxysilane (2 mole % based on the PEI recurringunit weight) and 0.064 g glycidyl 4-nonylphenylether (0.1 mole % basedon the PEI recurring unit weight). The mixture is heated at 75° C. for 5hours to give a polymeric reaction product. Aqueous NaOH solution (20g/L) is then added to make a 10% solution of the sodium salt.

Products U and V are made in a similar fashion to Product T, except that0.128 g glycidyl 4-nonylphenylether (0.2 mole % based on the PEIrecurring unit weight) is used to make Product U, and 0.32 g glycidyl4-nonylphenylether (0.5 mole % based on the PEI recurring unit weight)is used to make product V, instead of the amount of glycidyl4-nonylphenylether used to make Product T.

Tests comparing Products S, T, U and V (Table 6) in accordance with TestProcedure A show that the relatively more hydrophobic Products E, F andG give significantly better reduction in the amount of sodaliteprecipitated, and that products containing relatively low levels ofnonylphenyl (NP) provide improved performance.

TABLE 6 % Sodalite Precipitated Product Dose No. (% NP) 10 ppm 5 ppm 3ppm 6A* S (0) 5.0 22.6 43.5 6B T (0.1) 0.2 15.0 26.8 6C U (0.2) 0 12.725.4 6D V (0.5) 0 6.6 20.7

Examples 7-15

20.0 g of triethylenetetramine (TETA) is dissolved in a mixture of 50 mlof deionized water and 2.0 g of 50% sodium hydroxide. While stirring,7.8 g of glycidyloxypropyltrimethoxysilane is added dropwise and theresulting mixture stirred for one hour. Then 10.1 gm of epichlorohydrin(Epi) is added dropwise. The temperature is held below 30° C. by coolingin an ice bath. After completion of an exotherm, 14.6 gm of 50% sodiumhydroxide is added dropwise, with cooling to hold the temperature below30° C. to give a polymeric reaction product (Example 7).

The polymer products of Examples 8-15 are prepared in a similar manner,except: In Examples 8-11 and 13, about a third (on molar basis) of thetriethylenetetramine is replaced with 1,8-diaminooctane (Example 8),diaminoisophorone (Example 9), 1,2-diaminoethane (Example 10),1,3-diaminopropane (Example 11) or 1,6-diaminohexane (Example 13); inExample 12, 20.0 gm of triethylenetetramine is first reacted with 0.2mole (based on TETA and Epi) of glycidylnonylphenol (GNP) for 5 hrs at80° C. before being reacted with the epichlorohydrin, sodium hydroxideand glycidyloxypropyltrimethoxysilane; and in Examples 14 and 15, theTETA is replaced with N,N′-bis(3-aminopropyl)ethylenediamine (BAPED) andN,N′-bis(3-aminopropyl)-1,3-propanediamine (BAPPD), respectively. Thecompositions of the resulting polymers are shown in Table 7A. The “mole%” values are expressed as percentages of total polymer backbone monomer(sum of all amines and epichlorohydrin).

TABLE 7A Polymer compositions Oligo- Total polymer Exam- meric MolesMole % Moles Mole % Mole Mole % backbone Moles Moles Mole % ple amineDiamine Tetramine Tetramine Diamin Diamin Epi Epi moles GNP silanesilane 7 TETA None 1 55.56 0.00 0.80 44.44 1.80 0.24 13.33 8 TETA1,8-diaminooctane 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.24 11.43 9 TETAdiaminoisophorone 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.24 11.43 10TETA 1,2-diaminoethane 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.24 11.4311 TETA 1,3-diaminopropane 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.2411.43 12 TETA none 1 55.56 0.00 0.80 44.44 1.80 0.20 0.24 13.33 13 TETA1,6-diaminohexane 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.24 11.43 14BAPED none 1 55.56 0.00 0.80 44.44 1.80 0.24 13.33 15 BAPPD none 1 55.560.00 0.80 44.44 1.80 0.24 13.33 TETA = triethylenetetramine BAPED =N,N′-Bis(3-aminopropyl)ethylenediamine BAPPD =N,N′-Bis(3-aminopropyl)-1,3-propanediamine Epi = Epichlorohydrin Example12 was prepared with 0.2 moles GMP

The polymers of Examples 7-15 comprise a recurring unit of the formula(I) and a recurring unit of the formula (II) in which E is—CH₂CH(OH)CH₂—, A¹ is CH₂CH(OH)CH₂—O—CH₂CH₂CH₂—, R″ is Na, and in whichA², T and Q are shown in Table 7B below.

TABLE 7B Polymer compositions Ex. A² T Q 7 none —(CH₂)₂— H 8 none—(CH₂)₈— + —(CH₂)₂— H 9 none Isophorone 5-(1,3,3- Htrimethylcyclohexylmethyl) + —(CH₂)₂— 10 none —(CH₂)₂— H 11 none—(CH₂)₃— + —(CH₂)₂— H 12 —CH₂CH(OH)CH₂—O— —(CH₂)₂— nonylphenyl 13 none—(CH₂)₆— + —(CH₂)₂— H 14 none —(CH₂)₃— + —(CH₂)₂— H 15 none —(CH₂)₃— H

Examples 16A-N

Tests comparing the polymer products of Examples 7-15 in accordance withTest Procedure A show (Table 8) that the relatively more hydrophobic ofExamples 7-15 generally give better reduction in the amount of sodaliteprecipitated. For these tests, the blank contains no polymer.

TABLE 8 % Sodalite Precipitated Dose Ex. Product 10 ppm 20 ppm 50 ppm300 ppm 16A Example 7 98 96 96 87 16B Example 8 31 2 4 16C Example 9 8046 31 16D Example 7 98 98 16E Example 10 98 97 92 16F Example 11 99 10097 16G Example 8 8 1 16H Example 9 58 5 16I Example 12 66 60 16J Example7 99 98 16K Example 8 11 1 16L Example 13 91 52 16M Example 14 24 1 16NExample 15 2 0

Examples 17-30

A difficult-to-treat synthetic liquor (representative of a high levelnuclear waste stream) is prepared by dissolving the appropriate salts inwater to provide the composition shown in Table 9.

TABLE 9 Liquor component Molarity OH⁻ 1.60 Al 0.50 Si 0.0156 NO₃ ⁻ 1.94NO₂ ⁻ 1.37 CO₃ ⁻ 0.31 C₂O₄ ⁻ 0.00345 PO₄ ³⁻ 0.016 K 0.0090 Cl 0.010 SO₄²⁻ 0.028

A series of hydrophobically modified polyethyleneimines are prepared ina manner similar to that described for Product B1 in Example 1 above,except that butyl chloride (Hydrophobe type: B), hexyl chloride(Hydrophobe type: H), or 4-nonylphenyl glycidyl ether (Hydrophobe type:GNP) are used in place of chlorooctane. Tests are conducted comparingthe performance of the resulting polymer products to one another, usingthe difficult-to-treat synthetic liquor described in Table 9, inaccordance with the test method described above. The results shown inTable 10 illustrate the utility of these polymer products for reducingthe amount of sodalite precipitated in this difficult-to-treat syntheticliquor. In Table 10, the Scale % is reported as a percentage of theblank in which no scale inhibitor was used.

TABLE 10 Silane content Hydrophobe type Dose Scale % vs Example mole %PEI MW and mole % mg/L Blank 17 4 25k B (5%) 300 9 18 4 25k B (11%) 30010 19 4 25k B (18%) 300 10 20 4 25k B (25%) 300 14 21 4 25k H (5%) 300 722 4 25k H (11%) 300 9 23 4 25k H (18%) 300 11 24 4 25k H (25%) 300 1225* 4 1.2k  None 300 99 26 4 1.2k  GNP (2%) 300 100 27 4 1.2k  GNP (5%)300 80 28 4 1.2k  GNP (10%) 300 4 29 4 1.2k  GNP (15%) 300 2 30 4 25kGNP (8%) 300 25

Examples 31-34

Polymer #1 is made in the same manner as Product C in Example 2, exceptthat twice as much glycidyl 4-nonylphenyl ether (2 mole % based on thePEI unit weight) is used.

Polymer #2 is made in the same manner as Product C in Example 2, exceptthat glycidyl 2-ethylhexyl ether (2 mole % based on the PEI unit weight)is used instead of glycidyl 4-nonylphenyl ether.

Polymer #3 is made in the same manner as Product C in Example 2, exceptthat glycidyl octyl/decyl ether (2 mole % based on the PEI unit weight)is used instead of glycidyl 4-nonylphenyl ether.

Tests comparing Products #1, #2 and #3 with Product A are conducted inaccordance with Test Procedures A and C (Table 11). The results showthat the relatively more hydrophobic polymers of Examples 31-33 providesignificantly better reductions in scale than the less hydrophobicProduct A for both of the difficult-to-treat liquors.

TABLE 11 % Sodalite Precipitated Test Procedure A B No. Product (5 ppmdose) (5 ppm dose) 31* A 20 46 32 Polymer #1 0 3.8 33 Polymer #2 0 0.134 Polymer #3 0.6 11.6

Examples 35-52

The products shown in Tables 12 and 13 below are made with the same PEIand in the same manner as Product F in Example 3, except the nonylphenylgroup is replaced with octyl/decyl (10 mole % vs. PEI) or 2-ethylhexyl(5 mole % vs. PEI), and the mole % of glycidoxypropyltrimethoxysilanevs. the PEI is varied as shown. The results of tests conducted on thesepolymers in accordance with Test Procedures A, B and C show that therelatively more hydrophobic polymers generally provide significantlybetter reductions in scale than the control polymers for all three ofthe difficult-to-treat liquors.

TABLE 12 % sodalite formed vs. blank (no reagent added) Test TestProcedure A Procedure C Dosage Hydrophobic 10 510 group (silane) 4 ppmppm ppm ppm Product D none (4% silane) 100 Product #4 10% octyl/decyl(4% silane) 0 4.7 3.3 Product #5 10% octyl/decyl (5% silane) 0 3.1 1.7Product #6 10% octyl/decyl (6% silane) 0 2.0 1.8 Product #7 10%octyl/decyl (8% silane) 0 2.3 0.4 Product F 5% nonylphenyl (4% silane) 08.2 0.2 Product K 5% nonylphenyl (6% silane) 1.8 8.0 0.7 Product #8 5%2-ethylhexyl (4% silane) 2.3 10.7 3.5 Product M 5% 2-ethylhexyl (6%silane) 0.6 4.2 0.9 Product #9 5% 2-ethylhexyl (8% silane) 4.0 5.9 1.1

TABLE 13 % sodalite formed vs. blank (no reagent added) Test TestProcedure A Procedure B Dosage Hydrophobic 10 5 10 group (silane) 4 ppmppm ppm ppm Product D none (4% silane) 100 Product #4 10% octyl/decyl(4% silane) 0 4.7 (7.2) Product #5 10% octyl/decyl (5% silane) 0 6.4 1.2Product #6 10% octyl/decyl (6% silane) 0 5.7 0 Product #7 10%octyl/decyl (8% silane) 0 0 0 Product K 5% nonylphenyl (6% silane) 1.8 00 Product M 5% 2-ethylhexyl (6% silane) 0.6 1.3 0 Product #9 5%2-ethylhexyl (8% silane) 4.0 5.9 1.1

Examples 53-104

Polymer products are made and tested as described in Examples 1-52above, except that potassium salts of the polymers are made byhydrolyzing with potassium hydroxide in place of sodium hydroxide.Similar results are achieved.

Examples 105-156

Polymer products are made and tested as described in Examples 1-52above, except that potassium salts of the polymers are made byhydrolyzing with ammonium hydroxide in place of sodium hydroxide.Similar results are achieved.

It will be appreciated by those skilled in the art that variousmodifications and changes can be made without departing from the scopeof the embodiments disclosed herein. Such modifications and changes areintended to fall within the scope of the embodiments disclosed herein,as defined by the appended claims.

What is claimed is:
 1. A method of treating scale in a process streamcomprising: intermixing with a process stream a composition comprising apolymeric reaction product of a polyamine, a first nitrogen-reactivecompound, and a second nitrogen-reactive compound, the polymericreaction product having a weight average molecular weight of at least500, wherein the composition is present in an amount effective to reduceor eliminate scale in the process stream, wherein the firstnitrogen-reactive compound comprises a —Si(OR)₃ group and anitrogen-reactive group, wherein R is H, optionally substituted C₁-C₂₀alkyl, optionally substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀aralkyl, optionally substituted C₂-C₂₀ alkenyl, Group I metal ion, GroupII metal ion, or NR¹ ₄, wherein each R¹ is independently selected fromH, optionally substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂aryl, optionally substituted C₇-C₂₀ aralkyl, and optionally substitutedC₂-C₂₀ alkenyl; wherein the second nitrogen-reactive compound comprisesa nitrogen-reactive group and does not contain a —Si(OR)₃ group; whereinat least one of the polyamine and the second nitrogen-reactive compoundcomprises an optionally substituted hydrocarbyl radical comprising from2 to 40 carbons; and wherein the process stream comprises at least oneof a sulfate level of at least 1 g/L, a iron oxide level of at least 20mg/L, a sodalite level of at least 20 mg/L, and a combinednitrate/nitrite concentration of at least 0.5 molar.
 2. The methodaccording to claim 1, wherein the polymeric reaction product comprises aunit of formula (I) and a unit of formula (II):

wherein T and E are each independently a first optionally substitutedhydrocarbyl radical comprising from 2 to 40 carbons; Q is H or a secondoptionally substituted hydrocarbyl radical comprising from 1 to 20carbons; A¹ and A² are each independently a direct bond or an organicconnecting group comprising from 1 to 20 carbons; and R″ is H,optionally substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂ aryl,optionally substituted C₇-C₂₀ aralkyl, optionally substituted C₂-C₂₀alkenyl, Group I metal ion, Group II metal ion, or NR¹ ₄, wherein eachR¹ is independently selected from H, optionally substituted C₁-C₂₀alkyl, optionally substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀aralkyl, and optionally substituted C₂-C₂₀ alkenyl.
 3. The methodaccording to claim 2, wherein the polymeric reaction product comprisinga unit of formula (I) and a unit of formula (II) comprises at least oneof the following provisos: a first proviso wherein when A²-Q is H, atleast one of T and E comprises four or more carbon atoms; a secondproviso wherein when A²-Q is not H, at least one of T and E comprisestwo or more carbon atoms; a third proviso wherein Q does not contain aSi(OR)₃ group; a fourth proviso wherein A² is not unsubstituted—C(═O)-alkyl; and a fifth proviso wherein when Q is OH or NH₂, A¹ and A²are not both alkylene.
 4. The method according to claim 1, wherein theprocess stream is selected from the group consisting of a Bayer processstream, boiler water, a nuclear waste process stream, and a papermakingprocess stream.
 5. The method according to claim 4, wherein the processstream is a Bayer process stream.
 6. The method according to claim 1,wherein the scale is at least aluminosilicate scale and the amount ofcomposition that is effective to reduce or eliminate aluminosilicatescale in the process stream is in the range of 1 ppm to 500 ppm byweight, based on the process stream.
 7. The method according to claim 1,wherein R is a Group I metal ion, Group II metal ion, or NR¹ ₄.
 8. Themethod according to claim 1, wherein the process stream comprises atleast 1 g/L of sodium sulfate.
 9. The method according to claim 1,wherein the process stream comprises at least 20 mg/L of iron oxide. 10.The method according to claim 1, wherein the process stream comprises atleast 20 mg/L of sodalite.
 11. The method according to claim 1, whereinthe process stream has a combined nitrate/nitrate concentration of atleast 0.5 molar.
 12. The method according to claim 1, wherein thepolyamine comprises a unit of the formula —(CH₂)_(r)—NR²—, wherein r isan integer from 1 to 20, and R² is H, optionally substituted C₁-C₂₀alkyl, optionally substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀aralkyl, or optionally substituted C₂-C₂₀ alkenyl.
 13. The methodaccording to claim 1, wherein the polyamine comprises a (NR⁴ ₂)-J-(NR⁴₂) moiety; J is an optionally substituted hydrocarbyl fragmentcomprising from 2 to 40 carbons; and each R⁴ is independently H,optionally substituted C₁-C₈ alkyl, or optionally substituted C₆-C₁₀aryl.
 14. The method according to claim 13, wherein the secondnitrogen-reactive compound comprises at least two nitrogen-reactivemoieties.
 15. The method according to claim 1, wherein the polyamine isselected from polyethyleneimine, triethylenetetramine,1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane;1,5-diaminopentane, 1,5-diaminohexane, 1,8-diaminooctane anddiaminoisophorone; the first nitrogen-reactive compound is selected fromglycidoxypropyl trimethoxysilane and chloropropyl trimethoxysilane; andthe second nitrogen-reactive compound is selected from dimethylsulfate,chlorooctane, chlorohexane, benzyl chloride, epichlorohydrin, glycidyl4-nonylphenylether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,phenyl glycidyl ether, C₁₂-C₁₄ alkyl glycidyl ether, cresyl glycidylether, octenylsuccinic anhydride and octadecenylsuccinic anhydride. 16.The method according to claim 1, wherein the first nitrogen-reactivecompound is glycidoxypropyl trimethoxysilane.
 17. The method accordingto claim 1, wherein the second nitrogen-reactive compound is chosen fromC₁-C₂₀ alkyl halides, alkenyl halides, aralkyl halides, alkyl sulfates,glycidyl alcohols, glycidyl phenols, and glycidyl amines, and compoundscontaining an anhydride group.
 18. The method according to claim 17,wherein the second nitrogen-reactive compound is chosen fromdimethylsulfate, chlorooctane, chlorohexane, benzyl chloride,epichlorohydrin, glycidyl 4-nonylphenylether, butyl glycidyl ether,2-ethylhexyl glycidyl ether, phenyl glycidyl ether, C₁₂-C₁₄ alkylglycidyl ether, cresyl glycidyl ether, octenylsuccinic anhydride andoctadecenylsuccinic anhydride.
 19. A method for reducing or eliminatingscale in an industrial process comprising: adding to the process, acomposition comprising a polymeric reaction product of a polyamine, afirst nitrogen-reactive compound, and a second nitrogen-reactivecompound, the polymeric reaction product having a weight averagemolecular weight of at least 500, wherein the composition is present inan amount effective to reduce or eliminate scale in the process, whereinthe first nitrogen-reactive compound comprises a —Si(OR)₃ group and anitrogen-reactive group, wherein R is H, optionally substituted C₁-C₂₀alkyl, optionally substituted C₆-C₁₂ aryl, optionally substituted C₇-C₂₀aralkyl, optionally substituted C₂-C₂₀ alkenyl, Group I metal ion, GroupII metal ion, or NR¹ ₄, wherein each R¹ is independently selected fromH, optionally substituted C₁-C₂₀ alkyl, optionally substituted C₆-C₁₂aryl, optionally substituted C₇-C₂₀ aralkyl, and optionally substitutedC₂-C₂₀ alkenyl; wherein the second nitrogen-reactive compound comprisesa nitrogen-reactive group and does not contain a —Si(OR)₃ group; whereinat least one of the polyamine and the second nitrogen-reactive compoundcomprises an optionally substituted hydrocarbyl radical comprising from2 to 40 carbons.
 20. The method according to claim 19, wherein the scaleis at least aluminosilicate scale.